KR101613260B1 - Sulfonate based monomer, method for preparing the same, polymer derived from the monomer, polymer electrolyte membrane comprising the polymer, and fuel cell comprising the membrane - Google Patents

Abstract

There is provided a sulfonate monomer selected from the group consisting of a monomer represented by the following formula (1) and a structural isomer thereof:

≪ Formula 1 >

Wherein A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ , A ₁₀ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ refer to the detailed description of the invention.

Fuel cell

Description

The present invention relates to a sulfonate based monomer, a method for preparing the same, a polymer of the monomer, a polymer electrolyte membrane including the polymer, and a fuel cell employing the same. the polymer, and the fuel cell comprising the membrane,

The present invention relates to a sulfonate monomer, a process for producing the same, a polymer of the monomer, a polymer electrolyte membrane containing the polymer, and a fuel cell employing the polymer electrolyte membrane, and more particularly to a sulfonate monomer having a novel structure, A polymer of the monomer, a polymer electrolyte membrane containing the polymer, and a fuel cell employing the polymer electrolyte membrane.

The fuel cell can be classified into a polymer electrolyte membrane fuel cell (PEMFC), a phosphoric acid fuel cell (PAFC), a molten carbonate fuel cell (MCFC), a solid oxide And a solid oxide fuel cell (SOFC). The operating temperature of the fuel cell, the material of the component parts, and the like depend on the type of electrolyte used. PEMFC (Polymer Electrolyte Membrane Fuel Cell) has superior power, lower operating temperature, and faster response characteristics than other fuel cells.

Fuel cells are divided into fuel direct supply type or internal reforming type according to the manner in which fuel is supplied to the anode. Direct methanol fuel cell (DMFC) is a typical direct fuel supply type. A direct methanol fuel cell uses a polymer electrolyte membrane as an electrolyte and therefore belongs to a polymer electrolyte fuel cell. Since direct methanol fuel cell uses methanol as fuel, it does not use a hydrogen reformer, and because it operates at a low temperature, it is possible to construct a system simple and compact, which is suitable as a power source for small devices and portable devices.

A fuel cell is composed of a power generation unit, a reformer, a fuel tank, and a fuel pump, in which electricity is generated. The power generation portion forms the main body of the fuel cell, and the fuel pump supplies the fuel in the fuel tank to the reformer. Hydrogen gas is generated through the reformer and fuel is supplied to the power generation unit by the pump to generate electric energy by electrochemical reaction. The power generation unit may include a membrane electrode assembly (MEA) composed of an anode, a cathode, and a polymer electrolyte membrane.

As the electrolyte membrane of the polymer electrolyte fuel cell, a functional hydrogen ion exchange membrane having a cation exchange ability is used. Commercially, a hydrophobic ion exchange membrane containing a sulfonic acid group is mainly used. This is because the acidity of the sulfonic acid group is very large and the C-S bond is stable even under the oxidizing conditions. In the proton exchange membrane where sulfonic acid groups are present, water molecules must be present together to maintain the proton conductivity. In the presence of water molecules, the sulfonic acid groups present in the electrolyte membrane dissociate into sulfonate anions and hydrogen ions, and hydrogen ions migrate by the gradient of hydrogen ion concentration or electric field as in the case of sulfuric acid solution electrolytes. The hydrogen ion conductivity is affected by the number of sulfonic acid groups contained in the polymer electrolyte membrane, the structure of the polymer electrolyte membrane, and the amount of water contained in the polymer electrolyte membrane.

As a method for producing a hydrocarbon-based polymer electrolyte membrane in which a sulfonate group is substituted, there are a direct copolymerization method in which a sulfonated monomer is used and a method in which a polymer is synthesized and then a sulfonate group is introduced using a sulfonating agent and postsulfonation. Direct copolymerization is advantageous in that the content of sulfonate groups substituted in the polymer backbone structure can be easily controlled. Conventional sulfonate-introduced monomers include 3,3'-disulfonated-4,4'-dichlorodiphenylsulfone, 3,3'-disulfonated-4,4'-difluorodiphenylsulfone, 5,5'-carbonylbis (2-fluorobenzenesulfonate) and the like, and the production process is complicated or expensive.

Therefore, there is still a demand for a monomer having a sulfonate group introduced in a new structure which is easy to manufacture, cheap, and can be used for the production of a polymer electrolyte membrane of a fuel cell.

One aspect of the present invention is to provide a sulfonate-based monomer having a novel structure.

Another aspect of the present invention is to provide a method for producing the monomer.

Another aspect of the present invention is to provide a polymer obtained by polymerizing the sulfonate-based monomer.

Another aspect of the present invention is to provide a polymer electrolyte membrane comprising the polymer.

Another aspect of the present invention is to provide a fuel cell employing the above polymer electrolyte membrane.

According to one aspect of the present invention, there is provided a sulfonate monomer selected from the group consisting of a monomer represented by the following Formula 1 and a stereoisomer thereof:

≪ Formula 1 >

In this formula,

A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ , and A ₁₀ are each independently hydrogen or a halogen atom;

And R _1, R _2, R _3, R _4, R _5, R _6, R _7, R _8, R ₉ and R ₁₀ are independently hydrogen, -SO ₃ M, or -OA-SO ₃ M from each other, wherein A is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylalkylene group having 6 to 20 carbon atoms, or a heteroarylene group having 2 to 20 carbon atoms, Metal or hydrogen;

Provided that at least one of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ is a halogen atom and at least one of A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ is a halogen atom and R ₁ , At least one of R ₂ , R ₃ , R ₄ and R ₅ is -SO ₃ M or -OA-SO ₃ M and at least one of R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ is -SO a ₃ M, or -OA-SO ₃ M.

According to another aspect of the present invention,

Reacting a compound represented by the following formula (4a) to prepare a compound represented by the following formula (4b); And

Reacting a compound represented by the following formula (4b) with a sulfonate-based compound to prepare a compound represented by the following formula (4c): < EMI ID =

≪ Formula 4a &

&Lt; Formula 4b > < Formula 4c >

In the above equations,

A ₂₀ is a halogen atom;

A is an alkylene group having 1 to 20 carbon atoms or an alkylarylene group having 6 to 20 carbon atoms, and M is an alkali metal or hydrogen.

According to another aspect of the present invention,

Reacting a compound represented by the following formula (5a) to prepare a compound represented by the following formula (5b); And

Reacting a compound represented by the following formula (5b) with a sulfonate-based compound to prepare a compound represented by the following formula (5c): &lt; EMI ID =

&Lt; Formula 5a &

&Lt; Formula 5b > < Formula 5c >

In the above equations,

A ₂₀ is a halogen atom, and M is an alkali metal or hydrogen.

According to another aspect of the present invention,

A monomer according to the above; And

Alternatively, it is possible to use bisphenol A, 4,4-biphenol, hydroquione, 2,2-bis (4-hydroxyphenyl) -hexafluoropropane (2,2 (4-hydroxyphenyl) -hexafluoropropane, 4,4'-dichlorophenylsulfone, 4,4'-difluorophenylsulfone, and 4,4'- And at least one monomer selected from the group consisting of 4'-difluorobenzophenone.

According to still another aspect of the present invention, there is provided a polymer electrolyte membrane comprising the polymer.

According to another aspect of the present invention, there is provided a fuel cell employing the polymer electrolyte membrane.

According to one aspect of the present invention, the sulfonate monomer of the new structure is easy to produce, has a low production cost, and can contain a plurality of sulfonate groups, thereby realizing a high performance polymer electrolyte membrane for a fuel cell.

Hereinafter, a sulfonate-based monomer, a method for producing the same, a polymer of the monomer, a polymer electrolyte membrane including the polymer, and a fuel cell employing the same will be described in detail.

The sulfonate monomer according to an embodiment of the present invention is one selected from the group consisting of a monomer represented by the following formula (1) and a stereoisomer thereof:

&Lt; Formula 1 >

In this formula,

A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ , and A ₁₀ are each independently hydrogen or a halogen atom; And R _1, R _2, R _3, R _4, R _5, R _6, R _7, R _8, R ₉ and R ₁₀ are independently hydrogen, -SO ₃ M, or -OA-SO ₃ M from each other, wherein A is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylalkylene group having 6 to 20 carbon atoms, or a heteroarylene group having 2 to 20 carbon atoms, Metal or hydrogen; Provided that at least one of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ is a halogen atom and at least one of A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ is a halogen atom and R ₁ , At least one of R ₂ , R ₃ , R ₄ and R ₅ is -SO ₃ M or -OA-SO ₃ M and at least one of R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ is -SO a ₃ M, or -OA-SO ₃ M. When there are a plurality of -SO ₃ M or -OA-SO ₃ M, the M may be different from each other.

The monomers may have isomers depending on their structure. For example, cis and / or trans.

The monomer includes a plurality of halogen atoms and a plurality of sulfonate functional groups in the molecule. Therefore, the monomer can be polymerized by a nucleophilic substitution reaction or the like by including a highly reactive halogen atom. In addition, since the monomer includes a sulfonate group having a high degree of dissociation, the polymer obtained by polymerizing the monomer can be used as a proton exchange membrane or the like.

Further, the monomers are commercially available and can be produced at low cost, which is very advantageous commercially. In addition, since a plurality of sulfonic acid groups are contained, a high-performance polymer electrolyte membrane can be produced. For example, when the polymer electrolyte membrane for a fuel cell is manufactured, the performance of the electrolyte membrane can be improved by inducing an effective phase separation of the hydrophobic water and the hydrophobic portion.

The alkylene groups may be straight-chain or branch-type, which is a divalent group having an aliphatic chain system. The arylene group is a divalent group having an aromatic ring system, and may include two or more ring systems, and the two or more ring systems may exist in a bonded or fused form to each other. The heteroaryl group refers to a group in which at least one of the aryl groups is substituted with at least one member selected from the group consisting of N, O, S, and P.

The sulfonate-based monomer according to another embodiment of the present invention may be represented by the following general formulas (2a) to (2d):

&Lt; Formula 2a > < EMI ID =

(2c) < Formula (2d) >

In the above equations,

A ₁₁ and A ₁₂ are halogen atoms; A is an alkylene group having 1 to 20 carbon atoms or an alkylarylene group having 6 to 20 carbon atoms, and M is an alkali metal or hydrogen. Further, in one monomer, A and M may be different from each other.

The sulfonate-based monomer according to another embodiment of the present invention may be represented by the following formulas (3a) to (3h):

&Lt; EMI ID =

&Lt; Formula 3c > < EMI ID =

&Lt; Formula 3e > < EMI ID =

<Formula 3g> <Formula 3h>

The method for preparing a sulfonate monomer according to another embodiment of the present invention comprises the steps of: reacting a compound represented by the following formula (4a) to prepare a compound represented by the following formula (4b); And reacting a compound represented by the following formula (4b) with a sulfonate-based compound to prepare a compound represented by the following formula (4c): &lt; EMI ID =

&Lt; Formula 4a &

&Lt; Formula 4b > < Formula 4c >

In the above formulas, A ₂₀ is a halogen atom; A is an alkylene group having 1 to 20 carbon atoms, M is an alkali metal or hydrogen, and M may be different from each other.

Two molecules of the compound represented by Formula 4a are bonded by Mcmurry coupling to obtain the compound represented by Formula 4b. The compound represented by Formula 4b reacts with a sulfonate compound to introduce a sulfonate group into the molecule. Specifically, the sulfonate-based compound may be 1,3-propane sultone, 2-bromo-1-ethanesulfonic acid sodium salt, 4-bromo-1-butanesulfonic acid sodium salt, 7- Chloro-1-heptanesulfonic acid sodium salt, 4-chlorobenzenesulfonic acid salt and 4-bromopropanesulfonic acid sodium salt. However, the present invention is not limited thereto, Any compound can be used as long as it contains a sulfonate group as a compound that can be used in the technical field.

The above process is simple in two steps, and it is possible to produce a high performance sulfonate monomer containing a plurality of sulfonate groups in comparison with the production cost. In particular, the low cost of performance versus performance has a significant commercial advantage.

A method for preparing a sulfonate monomer according to another embodiment of the present invention comprises: reacting a compound represented by Formula 5a to prepare a compound represented by Formula 5b; And reacting a compound represented by the following formula (5b) with a sulfonate-based compound to prepare a compound represented by the following formula (5c): &lt; EMI ID =

&Lt; Formula 5a &

&Lt; Formula 5b > < Formula 5c >

In the above formulas, A ₂₀ is a halogen atom, M is an alkali metal or hydrogen, and M may be different from each other.

Two molecules of the compound represented by Formula 5a are bonded by Mcmurry coupling to obtain a compound represented by Formula 5b. The compound represented by Formula 5b reacts with a sulfonate compound to introduce a sulfonate group into the molecule. Specifically, it is preferable that the sulfonate compound is composed of SO ₃ , chlorosufonic acid, fuming SO ₃ , fuming SO ₃ / TEP (triethylphosphate), acetyl sulfate and concentrated sulfuric acid , But it is not necessarily limited thereto, and any compound which can be used in the technical field and contains a sulfonate group can be used.

The above process is simple in two steps, and it is possible to produce a high performance sulfonate monomer containing a plurality of sulfonate groups in comparison with the production cost. In particular, the low cost of performance versus performance has a significant commercial advantage.

A polymer according to another embodiment of the present invention comprises the monomer; And optionally, at least one selected from the group consisting of bisphenol A, 4,4'-biphenol, hydroquione, 2,2-bis (4-hydroxyphenyl) -hexafluoropropane Dihydroxy monomers such as 2,2-bis (4-hydroxyphenyl) -hexafluoropropane; And 4,4'-dichlorophenylsulfone, 4,4'-difluorophenylsulfone, 4,4'-difluorobenzophenone (4,4'-difluorophenylsulfone) '-difluorobenzophenone), and the like; and at least one monomer selected from the group consisting of: The monomer to be selectively used is not particularly limited as long as it can be used in the art in addition to the monomer. The sulfonate-based polymer is a hydrocarbon-based polymer into which a sulfonate has been introduced, and it is possible to perform hydrogen ion exchange by the sulfonate group.

According to another embodiment of the present invention, the weight average molecular weight of the sulfonate polymer is preferably 10,000 to 200,000, more preferably 30,000 to 150,000. The weight average molecular weight range is suitable for achieving the object according to one embodiment of the present invention.

According to another embodiment of the present invention, there is provided a polymer electrolyte membrane comprising the sulfonate-based polymer. Since the polymer electrolyte membrane contains the sulfonate-based copolymer, the methanol permeability is low and the hydrogen ion conductivity is high. The water content is also excellent.

According to another embodiment of the present invention, there is provided a fuel cell employing the polymer electrolyte membrane. The fuel cell includes a cathode, an anode, and the polymer electrolyte membrane sandwiched therebetween.

The cathode and the anode are composed of a gas diffusion layer and a catalyst layer. The catalyst layer includes a metal catalyst that promotes oxidation of hydrogen and reduction of oxygen. The catalyst layer is made of platinum, ruthenium, osmium, platinum-osmium alloy, platinum-palladium alloy and platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni, And at least one selected from the group consisting of &lt; RTI ID = 0.0 &gt; In particular, it is preferable to include platinum, ruthenium, osmium, a platinum-ruthenium alloy, a platinum-osmium alloy, a platinum-palladium alloy, a platinum-cobalt alloy, a platinum-nickel alloy or a mixture thereof.

The metal catalyst is generally used while being supported on a carrier. The carrier may be a carbon-based material such as acetylene black or black salt; Or inorganic fine particles such as alumina and silica can be used.

The gas diffusion layer may be made of carbon paper or carbon cloth, but is not limited thereto. The gas diffusion layer plays the role of supporting the electrode for the fuel cell and diffuses the reaction gas into the catalyst layer to make the reaction gas easily accessible to the catalyst layer. The gas diffusion layer is preferably a carbon paper or a carbon cloth which has been subjected to a water-repellent treatment with a fluorine resin such as polytetrafluoroethylene. The water repellent treated carbon paper or carbon cloth can prevent the gas diffusion efficiency from being lowered due to water generated when the fuel cell is driven.

The electrode may further include a microporous layer for further enhancing a gas diffusion effect between the gas diffusion layer and the catalyst layer. The microporous layer may be formed by applying a conductive material such as carbon powder, carbon black, activated carbon, or acetylene black, a binder such as polytetrafluoroethylene, or a composition containing an ionomer according to the purpose of the fill.

According to another embodiment of the present invention, the fuel cell is preferably a direct methanol fuel cell. A schematic diagram of the direct methanol fuel cell is shown in FIG.

1, the direct methanol fuel cell includes an anode 32 to which a fuel is supplied, a cathode 30 to which an oxidizing agent is supplied, and an electrolyte membrane 41 that is disposed between the anode 32 and the cathode 30 ). The anode 32 includes an anode diffusion layer 22 and an anode catalyst layer 33. The cathode 30 includes a cathode diffusion layer 32 and a cathode catalyst layer 31. [

The methanol aqueous solution transferred to the anode catalyst layer 33 through the anode diffusion layer 22 is decomposed into electrons, hydrogen ions, carbon dioxide, etc. by the catalyst. The hydrogen ions are transferred to the cathode catalyst layer 31 through the electrolyte membrane 41, the electrons are transferred to the external circuit, and the carbon dioxide is discharged to the outside. In the cathode catalyst layer 31, hydrogen ions transferred through the electrolyte membrane, electrons supplied from the external circuit, and oxygen in the air supplied through the cathode diffusion layer 32 react to produce water.

Hereinafter, the present invention will be described in further detail with reference to preferred examples, but the present invention is not limited thereto.

(Preparation of sulfonate-based monomer)

Example 1

Sulfonate-based monomer (3) was prepared according to Reaction Scheme 1 below.

<Reaction Scheme 1>

Step 1: Mcmurry coupling

A condenser, a magnetic stirring bar, a dropping funnel and a solid addition tube were placed in a 250 mL three-necked flask, and the flask was purged with nitrogen, and titanium chloride (TiCl ₄ ) And 200 ml of dimethoxy ethane were added thereto. Subsequently, after the flask was immersed in an ice bath, 0.3 mol of lithium aluminum hydride (LiAlH ₄ ) was added dropwise over 30 minutes. Next, the temperature of the flask was raised to 90 DEG C, and the solvent was refluxed for 2 hours. Subsequently, the flask was cooled to room temperature, and a solution obtained by dissolving 0.2 mol of 4-chloro-4'-hydroxybenzophenone (1) in 100 ml of dimethoxyethane was added thereto, Was added dropwise at room temperature for 30 minutes. Thereafter, the flask was refluxed for 3 hours to terminate the reaction. Water was added to the flask to remove unreacted titanium chloride and lithium. Subsequently, the reaction solution was extracted with dimethyl ether, and then residual water was removed using magnesium sulfate. Then, the product (2) was isolated using column chromatography (yield: 80% or more).

GC-Mass: 216 (40) , 431 (M +, 100), 433 (M + +2,40), 435 (M + +4,15)

Step 2: Introduction of sulfonate groups

A magnetic stir bar and a dropping funnel were placed in a 250 mL two-necked flask, and after replacing with nitrogen, 0.2 mol of the product (2) obtained in the first step was dissolved in 400 mL of dimethylacetamide, It melted together. Subsequently, 0.5 mol of sodium methoxide and 0.5 mol of 1,3-propane sultone were added to the flask, and the mixture was reacted at 60 DEG C for 12 hours. After the reaction, hydrochloric acid was added to the flask to make the reaction solution pH 7, followed by vacuum drying at 40 ° C. The dried reaction product was recrystallized using water and isopropyl alcohol to obtain the final product (3) (yield: 70% or more).

^{1 H-NMR (400MHz DMSO-} d 6, ppm): δ7.1 (C 6 H 4 Cl, 4H), δ7.04, 6.94 (phenyl ring, 8H), δ6.58 (C 6 H 4 O, 8H _{), δ4.20 (OCH 2 CH 2} CH 2 SO 3 Na, 2H), δ2.59 (OCH 2 CH 2 CH 2 SO 3 Na, 2H), δ2.04 (OCH 2 CH 2 CH 2 SO 3 Na, 2H)

Example 2

Sulfonate-based monomers were prepared in the same manner as in Example 1, except that 5-chloro-2'-hydroxybenzophenone was used instead of 4-chloro-4'-hydroxybenzophenone in the first step.

Example 3

A sulfonate monomer (7) was prepared according to the following Reaction Scheme 2.

<Reaction Scheme 2>

Step 1: Mac Head Coupling

A condenser, a magnetic stirring bar, a dropping funnel and a solid addition tube were placed in a 250 mL three-necked flask, and the mixture was substituted with nitrogen, and titanium chloride (TiCl ₄ ) 0.3 mol, and dimethoxy ethane (200 ml). Subsequently, after the flask was immersed in an ice bath, 0.3 mol of lithium aluminum hydride (LiAlH4) was added dropwise over 30 minutes. Next, the temperature of the flask was raised to 90 DEG C, and the solution was refluxed for 2 hours. Subsequently, the flask was cooled to room temperature, and a solution of 0.2 mol of 4-chlorobenzophenone (4) in 100 ml of dimethoxyethane was added dropwise at room temperature for 30 minutes. Thereafter, the flask was refluxed for 3 hours to terminate the reaction. Water was added to the reaction solution to remove unreacted titanium chloride and lithium. Subsequently, the reaction solution was extracted with dimethyl ether, and then residual water was removed using magnesium sulfate. The product (5) was isolated by column chromatography (yield: 75% or more).

GC-Mass: 252 (30) , 330 (20), 400 (M +, 100), 402 (M + +2,60), 404 (M + +4,15)

Step 2: Introduction of sulfonate groups

A 250 mL two-necked flask was equipped with a magnetic stirring bar and a dropping funnel. The flask was purged with nitrogen, and 0.2 mol of the product (5) obtained in the first step was added with 400 mL of chloroform Melted. Subsequently, 0.3 mol of chlorosulfonic acid was added dropwise to the flask using a dropping funnel for 1 hour, followed by reaction at room temperature for 12 hours. After the reaction, the reaction product was filtered in the flask, the filtrate was dried at 40 ° C and the non-reactant was removed using isopropyl alcohol. Subsequently, the filtrate from which the unreacted material was removed was dissolved in water, adjusted to pH 7 with an aqueous solution of NaOH, and then vacuum-dried at 40 ° C. The dried reaction product was recrystallized using water and isopropyl alcohol to obtain the final product (7) (yield: 70% or more).

^{1 H-NMR (400MHz DMSO-} d 6, ppm): δ7.39 (C 6 H 4 SO 3 Na, 4H), δ7.20 (C 6 H 4 Cl, 4H), 6.94 (phenyl ring, 8H)

Example 4

A sulfonate-based monomer was prepared in the same manner as in Example 3, except that 3-chlorobenzophenone was used instead of 4-chlorobenzophenone in the first step.

Example 5

A sulfonate-based monomer was prepared in the same manner as in Example 3 except that 2-chlorobenzophenone was used instead of 4-chlorobenzophenone in the first step.

1 is a schematic diagram of a direct methanol fuel cell according to one embodiment of the present invention.

Claims (10)

A sulfonate monomer selected from the group consisting of a monomer represented by the following formula (1) and a stereoisomer thereof: &Lt; Formula 1 >

In this formula, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ , A ₈ , A ₉ , and A ₁₀ are each independently hydrogen or a halogen atom; And R _1, R _2, R _3, R _4, R _5, R _6, R _7, R _8, R ₉ and R ₁₀ are independently hydrogen, -SO ₃ M, or -OA-SO ₃ M from each other, wherein A is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylalkylene group having 6 to 20 carbon atoms, or a heteroarylene group having 2 to 20 carbon atoms, Metal or hydrogen; Provided that at least one of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ is a halogen atom and at least one of A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ is a halogen atom and R ₁ , At least one of R ₂ , R ₃ , R ₄ and R ₅ is -SO ₃ M or -OA-SO ₃ M and at least one of R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ is -SO a ₃ M, or -OA-SO ₃ M. The sulfonate monomer according to claim 1, wherein the monomer is represented by one of the following formulas (2a) and (2c): &Lt; EMI ID =

(2c)

In the above equations, A ₁₁ and A ₁₂ are halogen atoms; A is an alkylene group having 1 to 20 carbon atoms or an alkylarylene group having 6 to 20 carbon atoms, and M is an alkali metal or hydrogen. The sulfonate monomer according to claim 1, wherein the monomer is represented by one of the following formulas (3a), (3c), (3e) and (3g) &Lt; EMI ID =

&Lt; Formula 3c >

<Formula 3e>

<Formula 3g>

Reacting a compound represented by the following formula (4a) to prepare a compound represented by the following formula (4b); And Reacting a compound represented by the following formula (4b) with a sulfonate compound to prepare a compound represented by the following formula (4c): &lt; EMI ID = &Lt; Formula 4a &

&Lt; Formula 4b > < Formula 4c >

In the above equations, A ₂₀ is a halogen atom; A is an alkylene group having 1 to 20 carbon atoms or an alkylarylene group having 6 to 20 carbon atoms, and M is an alkali metal or hydrogen. 5. The method according to claim 4, wherein the sulfonate compound is at least one selected from the group consisting of 1,3-propanesultone, 2-bromo-1-ethanesulfonic acid sodium salt, 4-bromo-1-butanesulfonic acid sodium salt, Sulfonic acid sodium salt, 4-chlorobenzene sulfonate, and 3-bromopropanesulfonic acid sodium salt. Reacting a compound represented by the following formula (5a) to prepare a compound represented by the following formula (5b); And Reacting a compound represented by the following formula (5b) with a sulfonate compound to prepare a compound represented by the following formula (5c): &lt; EMI ID = &Lt; Formula 5a &

&Lt; Formula 5b > < Formula 5c >

In the above equations, A ₂₀ is a halogen atom, and M is an alkali metal or hydrogen. The process according to claim 6, wherein the sulfonate compound is selected from the group consisting of chlorosulfonic acid, fuming sulfuric acid, and fuming sulfuric acid triethyl phosphate. A monomer according to any one of claims 1 to 3; And Optionally, a mixture of bisphenol A, 4,4'-biphenol, hydroquione, 2,2-bis (4-hydroxyphenyl) -hexafluoropropane (2 2-bis (4-hydroxyphenyl) -hexafluoropropane, 4,4'-dichlorophenylsulfone, 4,4'-difluorophenylsulfone, And at least one monomer selected from the group consisting of 4'-difluorobenzophenone; and a sulfonate-based polymer obtained by polymerizing at least one monomer selected from the group consisting of 4'-difluorobenzophenone. 9. A polymer electrolyte membrane comprising the sulfonate polymer of claim 8. A fuel cell employing the polymer electrolyte membrane of claim 9.

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